US4665197A - Process for preparing azetidine derivatives and intermediates thereof - Google Patents
Process for preparing azetidine derivatives and intermediates thereof Download PDFInfo
- Publication number
- US4665197A US4665197A US06/743,735 US74373585A US4665197A US 4665197 A US4665197 A US 4665197A US 74373585 A US74373585 A US 74373585A US 4665197 A US4665197 A US 4665197A
- Authority
- US
- United States
- Prior art keywords
- acid
- azetidine
- formula
- carboxylic acid
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract 3
- 239000000543 intermediate Substances 0.000 title abstract description 4
- 150000001539 azetidines Chemical class 0.000 title 1
- 239000002253 acid Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- GFZWHAAOIVMHOI-UHFFFAOYSA-N azetidine-3-carboxylic acid Chemical compound OC(=O)C1CNC1 GFZWHAAOIVMHOI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- IADUEWIQBXOCDZ-VKHMYHEASA-N (S)-azetidine-2-carboxylic acid Chemical compound OC(=O)[C@@H]1CCN1 IADUEWIQBXOCDZ-VKHMYHEASA-N 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- JPYDUTKQJQIRIA-UHFFFAOYSA-N 1-nitrosoazetidine-3,3-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CN(N=O)C1 JPYDUTKQJQIRIA-UHFFFAOYSA-N 0.000 abstract description 14
- LOKLKVWDANNUKQ-UHFFFAOYSA-N 1-nitrosoazetidine-3-carboxylic acid Chemical compound OC(=O)C1CN(N=O)C1 LOKLKVWDANNUKQ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- AOFFCJVJVZRCBL-UHFFFAOYSA-N [1-benzyl-3-(hydroxymethyl)azetidin-3-yl]methanol Chemical compound C1C(CO)(CO)CN1CC1=CC=CC=C1 AOFFCJVJVZRCBL-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- JAXQPBINKGFTPK-UHFFFAOYSA-N [3-(hydroxymethyl)azetidin-3-yl]methanol Chemical compound OCC1(CO)CNC1 JAXQPBINKGFTPK-UHFFFAOYSA-N 0.000 description 8
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- -1 3,3-bis(hydroxymethyl)-1-benzylazetidine acetone acetal Chemical class 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- GETUVALQSXUKQD-UHFFFAOYSA-N azetidine-3,3-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CNC1 GETUVALQSXUKQD-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- CEWDAROJZGKUGQ-UHFFFAOYSA-N 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane Chemical compound CC1(C)OCC(CBr)(CBr)CO1 CEWDAROJZGKUGQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PBRMCNKWJSRLMQ-UHFFFAOYSA-N [1-ethyl-3-(hydroxymethyl)azetidin-3-yl]methanol Chemical compound CCN1CC(CO)(CO)C1 PBRMCNKWJSRLMQ-UHFFFAOYSA-N 0.000 description 2
- SESXZSLSTRITGO-UHFFFAOYSA-N [3-(bromomethyl)oxetan-3-yl]methanol Chemical compound OCC1(CBr)COC1 SESXZSLSTRITGO-UHFFFAOYSA-N 0.000 description 2
- OYCHALDOCQCEOD-UHFFFAOYSA-N [3-(hydroxymethyl)-1-methylazetidin-3-yl]methanol Chemical compound CN1CC(CO)(CO)C1 OYCHALDOCQCEOD-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical compound C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010021929 Infertility male Diseases 0.000 description 1
- 208000007466 Male Infertility Diseases 0.000 description 1
- RMZRJFYTVCMNGQ-UHFFFAOYSA-N [3-(hydroxymethyl)-1-propan-2-ylazetidin-3-yl]methanol Chemical compound CC(C)N1CC(CO)(CO)C1 RMZRJFYTVCMNGQ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- VDFLYDCPHUPMAO-UHFFFAOYSA-N azetidine-3-carboxylic acid Chemical compound OC(=O)C1CNC1.OC(=O)C1CNC1 VDFLYDCPHUPMAO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006264 debenzylation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 208000021302 gastroesophageal reflux disease Diseases 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D205/00—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom
- C07D205/02—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D205/04—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
Definitions
- European Patent Application Publication No. 29265 discloses that 3-carboxyazetidine (azetidine-3-carboxylic acid) and related compounds are useful as plant hybridizing agents, based on their ability to produce male sterility in plants.
- azetidine-3-carboxylic acid can be prepared by the nitric acid oxidation of a 3,3-bis(hydroxymethyl)azetidine, of the formula ##STR2## wherein R represents a hydrogen atom or a group of the formula R 1 R 2 CH-- wherein R 1 and R 2 are independently selected from hydrogen, alkyl (preferably C 1-6 alkyl) and optionally substituted phenyl moieties, by treating the compound of Formula I with nitric acid at a temperature of from about 35° C. to the reflux temperature of the mixture, then subjecting the resulting initial azetidine carboxylic acid product to acid conditions at a temperature above about 80° C. to produce an acid-addition salt of azetidine-3-carboxylic acid, and thereafter, if desired, converting the acid addition salt to the free acid or a different salt of the acid.
- R represents a hydrogen atom or a group of the formula R 1 R 2 CH-- wherein R 1 and R 2 are independently selected
- Optional substituents on a phenyl moiety include one or more substituents selected from the group consisting of C 1-4 alkyl, halogen, and nitro moieties.
- R 1 and R 2 are hydrogen.
- R represents a hydrogen atom or a group of the formula R 1 CH 2 -- wherein R 1 represents hydrogen, a C 1-3 alkyl group or a phenyl group.
- the compound of formula I may conveniently be treated with nitric acid at a temperature in the range 35° C. to the reflux temperature of the reaction mixture, conveniently a temperature in the range 40° to 85° C. Temperatures in the range of 45° to 60° C. are very effective.
- the concentration of nitric acid used in the treatment of the compound of formula I be at least 40% w/w. Conveniently the concentration of the nitric acid used is in the range 50 to 60% w/w.
- the step of subjecting the initial product to acid conditions comprises treating the product with an aqueous acid selected from nitric, formic, acetic, hydrohalic (e.g. hydrochloric) and sulfuric acids.
- an aqueous acid selected from nitric, formic, acetic, hydrohalic (e.g. hydrochloric) and sulfuric acids. If nitric acid is used, its concentration is preferably 30% w/w or less.
- the initial product is preferably subjected to acid treatment at temperatures above 80° C., more preferably above 90° C. Conveniently the initial product is subjected to acid conditions at the reflux temperature of the reaction mixture.
- the azetidine-3-carboxylic acid product will generally exist as an acid-addition salt. If the acid is formic acid, it may be driven off with water when an aqueous solution is evaporated to dryness, to liberate the free acid. In other cases, acid-addition salts can readily be converted to the free acid, or to other acid-addition salts by conventional known methods.
- azetidine-3,3-dicarboxylic acid 1-nitrosoazetidine-3,3-dicarboxylic acid and 1-nitrosoazetidine-3-carboxylic acid.
- azetidine-3,3-dicarboxylic acid is the subject of Applicants' copending patent application (K-0057 US), and the present invention further comprises azetidine-3-carboxylic acid derivatives of the formula ##STR3## or salts thereof, wherein R 3 is hydrogen or --COOH.
- 7.5 g of 1A was taken up in 100 ml of 25% (w/w) aqueous ammonia and the mixture was stirred for 16 hours in an autoclave at 80° C. After evaporation of the aqueous ammonia, 10 ml of 48% (w/w) aqueous hydrobromic acid was added to the residue and the resulting solution was stirred at 60° C. After 2 hours the aqueous hydrobromic acid was evaporated, 75 ml of 25% (w/w) aqueous ammonia was added to the residue, and the resulting solution was stirred at 60° C. After 2 hours the aqueous ammonia was evaporated.
- 3,3-bis(hydroxymethyl)azetidine may be prepared by debenzylation of 3,3-bis(hydroxymethyl)-1-benzylazetidine using hydrogen over palladium on carbon catalyst in methanol.
- 3,3-Bis(hydroxymethyl)-1-methylazetidine was prepared by a process similar to that of Example 2 using methylamine instead of ammonia.
- 3,3-Bis(hydroxymethyl)-1-ethylazetidine was prepared by a process similar to that of Example 2 using ethylamine instead of ammonia.
- 3,3-bis(hydroxymethyl)-1-isopropylazetidine was prepared by a process similar to that of Example 2 using isopropylamine instead of ammonia.
- Example 3 3,3-bis(hydroxymethyl)-1-methylazetidine, and of Example 4, 3,3-bis(hydroxymethyl)-1-ethylazetidine, were oxidized under the conditions of Example 8(i), and in each case the product was 1-nitrosoazetidine-3,3-dicarboxylic acid.
- Example 8(ii) 1-Nitrosoazetidine-3,3-dicarboxylic acid was subjected to acid treatment following procedures comparable with that of Example 8(ii). Experimental conditions and results are given in Table 3 following. Comparative Example A demonstrates that acid conditions are necessary for full conversion, but demonstrates that 1-nitrosoazetidine-3-carboxylic acid is an intermediate in conversion of 1-nitrosoazetidine-3,3-dicarboxylic acid to azetidine-3-carboxylic acid.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Saccharide Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB848415615A GB8415615D0 (en) | 1984-06-19 | 1984-06-19 | Preparing azetidine derivatives |
| GB8415615 | 1984-06-19 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/859,663 Continuation-In-Part US4701534A (en) | 1984-06-19 | 1986-05-05 | Azetidine derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4665197A true US4665197A (en) | 1987-05-12 |
Family
ID=10562649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/743,735 Expired - Fee Related US4665197A (en) | 1984-06-19 | 1985-06-12 | Process for preparing azetidine derivatives and intermediates thereof |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4665197A (de) |
| EP (1) | EP0165636B1 (de) |
| JP (2) | JPS6112658A (de) |
| AT (1) | ATE36318T1 (de) |
| BR (1) | BR8502885A (de) |
| CA (1) | CA1223269A (de) |
| DE (1) | DE3564263D1 (de) |
| GB (1) | GB8415615D0 (de) |
| ZA (2) | ZA854545B (de) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4812581A (en) * | 1986-11-18 | 1989-03-14 | Shell Oil Company | Catalytic hydrogenolysis |
| AU599050B2 (en) * | 1985-09-30 | 1990-07-12 | Shell Internationale Research Maatschappij B.V. | A process for the preparation of an azetidine-3-carboxylic acid or salt thereof |
| US5055099A (en) * | 1987-09-14 | 1991-10-08 | International Technidyne Corporation | Apparatus and method for utilizing autotransfusion systems and related equipment |
| WO1994000447A1 (en) * | 1992-06-30 | 1994-01-06 | Pohang Iron & Steel Co., Ltd. | Novel cyclic lipid derivatives as potent paf antagonists |
| WO1996036602A1 (en) * | 1995-05-15 | 1996-11-21 | The United States Of America | Adnaz, compositions and processes |
| US5700817A (en) * | 1992-06-30 | 1997-12-23 | Pohang Iron & Steel Co., Ltd. | Cyclic lipid derivatives as potent PAF antagonists |
| CN106632395A (zh) * | 2016-11-30 | 2017-05-10 | 辽宁大学 | 一种螺环氨基酸酯类化合物及其制备方法和应用 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8509746D0 (en) * | 1985-04-16 | 1985-05-22 | Shell Int Research | Preparing azetidine derivatives |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1169027A (en) * | 1966-11-19 | 1969-10-29 | Beecham Group Ltd | Azetidine Derivatives |
| EP0029265A2 (de) * | 1979-11-16 | 1981-05-27 | Shell Internationale Researchmaatschappij B.V. | Verfahren zur Herstellung von Azetidinderivaten, diese enthaltende Zusammensetzungen mit sterilisierender Wirkung für männliche Pflanzenteile, deren Verwendung zur Sterilisation männlicher Teile in Pflanzen, Verfahren zur Herstellung von F1-Hybridsamen und bestimmte Azetidinderivate |
| EP0114079A1 (de) * | 1983-01-13 | 1984-07-25 | Shell Internationale Researchmaatschappij B.V. | Arylsulphonyl-azetidin-Verbindungen, ihre Herstellung und ihre Verwendung als Zwischenprodukte |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1479735A (fr) * | 1966-05-12 | 1967-05-05 | Novomoskovsky Anilinokrasochny | Procédé de fabrication de l'acide oxalique |
-
1984
- 1984-06-19 GB GB848415615A patent/GB8415615D0/en active Pending
-
1985
- 1985-05-23 CA CA000482142A patent/CA1223269A/en not_active Expired
- 1985-06-04 EP EP85200881A patent/EP0165636B1/de not_active Expired
- 1985-06-04 DE DE8585200881T patent/DE3564263D1/de not_active Expired
- 1985-06-04 AT AT85200881T patent/ATE36318T1/de not_active IP Right Cessation
- 1985-06-12 US US06/743,735 patent/US4665197A/en not_active Expired - Fee Related
- 1985-06-17 BR BR8502885A patent/BR8502885A/pt unknown
- 1985-06-17 JP JP60130088A patent/JPS6112658A/ja active Pending
- 1985-06-17 ZA ZA854545A patent/ZA854545B/xx unknown
- 1985-06-18 JP JP60130968A patent/JPS6112690A/ja active Pending
- 1985-06-18 ZA ZA854582A patent/ZA854582B/xx unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1169027A (en) * | 1966-11-19 | 1969-10-29 | Beecham Group Ltd | Azetidine Derivatives |
| EP0029265A2 (de) * | 1979-11-16 | 1981-05-27 | Shell Internationale Researchmaatschappij B.V. | Verfahren zur Herstellung von Azetidinderivaten, diese enthaltende Zusammensetzungen mit sterilisierender Wirkung für männliche Pflanzenteile, deren Verwendung zur Sterilisation männlicher Teile in Pflanzen, Verfahren zur Herstellung von F1-Hybridsamen und bestimmte Azetidinderivate |
| EP0114079A1 (de) * | 1983-01-13 | 1984-07-25 | Shell Internationale Researchmaatschappij B.V. | Arylsulphonyl-azetidin-Verbindungen, ihre Herstellung und ihre Verwendung als Zwischenprodukte |
| US4569795A (en) * | 1983-01-13 | 1986-02-11 | Shell Oil Company | Arylsulphonyl azetidine compounds, their preparation and their use as intermediates |
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| March, ed., Advanced Organic Chemistry, 2nd ed., (1977), McGraw-Hill, New York, pp. 569-572, 1107-1108. |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU599050B2 (en) * | 1985-09-30 | 1990-07-12 | Shell Internationale Research Maatschappij B.V. | A process for the preparation of an azetidine-3-carboxylic acid or salt thereof |
| US4812581A (en) * | 1986-11-18 | 1989-03-14 | Shell Oil Company | Catalytic hydrogenolysis |
| US5055099A (en) * | 1987-09-14 | 1991-10-08 | International Technidyne Corporation | Apparatus and method for utilizing autotransfusion systems and related equipment |
| WO1994000447A1 (en) * | 1992-06-30 | 1994-01-06 | Pohang Iron & Steel Co., Ltd. | Novel cyclic lipid derivatives as potent paf antagonists |
| US5610310A (en) * | 1992-06-30 | 1997-03-11 | Pohang Iron & Steel Co., Ltd | Cyclic lipid derivatives as potent PAF antagonists |
| US5700817A (en) * | 1992-06-30 | 1997-12-23 | Pohang Iron & Steel Co., Ltd. | Cyclic lipid derivatives as potent PAF antagonists |
| WO1996036602A1 (en) * | 1995-05-15 | 1996-11-21 | The United States Of America | Adnaz, compositions and processes |
| CN106632395A (zh) * | 2016-11-30 | 2017-05-10 | 辽宁大学 | 一种螺环氨基酸酯类化合物及其制备方法和应用 |
| CN106632395B (zh) * | 2016-11-30 | 2018-09-21 | 辽宁大学 | 一种螺环氨基酸酯类化合物及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0165636A1 (de) | 1985-12-27 |
| JPS6112658A (ja) | 1986-01-21 |
| EP0165636B1 (de) | 1988-08-10 |
| BR8502885A (pt) | 1986-02-25 |
| JPS6112690A (ja) | 1986-01-21 |
| ZA854582B (en) | 1986-04-30 |
| CA1223269A (en) | 1987-06-23 |
| ATE36318T1 (de) | 1988-08-15 |
| GB8415615D0 (en) | 1984-07-25 |
| DE3564263D1 (en) | 1988-09-15 |
| ZA854545B (en) | 1986-02-26 |
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